Mineralogical Magazine,August 2009,Vol. 73(4),pp. 645–671

Chemistry, textures and physical properties of À geological interpretation and technical application

J. GO¨ TZE* TU Bergakademie Freiberg, Institute of Mineralogy, Brennhausgasse 14, D-09596 Freiberg, Germany [Received 15 January 2009; Accepted 30 June 2009]

ABSTRACT Quartz is one of the most abundant in the Earth’s crust and the most important silica , occurring in large amounts in igneous, metamorphic and sedimentaryrocks. The mineral is widelyused as a raw material in several industrial applications. Because of its chemical composition (SiO2) and its specific properties, quartz can be used both as a bulk product (e.g. quartz sands in the glass or foundry industry) and as a high-tech material (e.g. piezo or optical quartz). Dependent on the specific conditions of either natural or synthetic formation, quartz can display typomorphic properties. Variations in crystal shape, specific micro-structure, trace element or isotope compositions, characteristic spectroscopic properties, etc. maybe controlled bythe genesis of the quartz involved. Accordingly, the defect structure of quartz is a fingerprint of its conditions of formation. A knowledge of the interrelation between quartz genesis and the specific properties developed at that time can be used both for the reconstruction of geological processes and for specific technical applications. Selected examples in the present studygive an overview of how to analyseand use the specific information inherent in the mineral quartz.

KEYWORDS: quartz, genesis, chemical composition, physical properties, technical application.

Introduction physical properties. Single crystals of quartz, THE various modifications of silica (SiO2) playan polycrystalline material and mono-mineralic important role in geological as well as industrial rocks are currentlyused in industry.The processes. Quartz is one of the most abundant application of quartz is widespread, including minerals in the Earth’s crust and the most use as a bulk product (e.g. high-purityquartz important silica mineral, occurring in large sands or ) and perfect natural crystals, as amounts in igneous, metamorphic and sedimen- well as a Si ore. Because of the increasing taryrocks (Table 1). Due to its highlystable requirements concerning the qualityof quartz raw nature, quartz is especiallyenriched in all materials, synthetic quartz crystals or silica siliciclastic sediments and rocks. For instance, materials are necessaryfor certain highly sandstones have an average content of 65% quartz advanced applications (Blankenburg et al., 1994). (Blatt et al., 1980) and quartz grains may The chemical and physical properties of quartz comprise 599% in some mature sands (Go¨tze, are determined byits actual, as opposed to its 1997). theoretical, structure. The type and frequency of In addition, natural quartz raw materials lattice defects are influenced bythe thermody- represent a complex group of industrial rocks namic conditions during mineralization. In addi- and minerals with interesting chemical and tion, subsequent processes such as changes in P-T conditions during hydrothermal or metamorphic processes, as well as natural irradiation or alteration, can change the original structure of * E-mail: [email protected] quartz. Dependent on these specific conditions of DOI: 10.1180/minmag.2009.073.4.645 formation, quartz can therefore be characterized

# 2009 The Mineralogical Society J. GO¨ TZE

TABLE 1. Abundance of quartz in the lithosphere (Ro¨sler, 1981).

Rock type Quartz content Relative proportion (1018 t) (%)

Magmatic rocks 8.05 93.6 Metamorphic rocks 0.28 3.2 Sedimentaryrocks 0.28 3.2 Lithosphere 8.60 100

by a typical crystal shape or certain growth quartz. Thus, complex investigations bya phenomena, a specific structure, a varying combination of different methods have the chemical composition and/or characteristic greatest potential for successful interpretation. physical properties. Accordingly, the real struc- Certain results illustrate that even the structure ture is a fingerprint of the genetic conditions. The and composition of single quartz crystals can be knowledge of the interrelation between quartz veryheterogeneous and yetbring a wealth of genesis and specific properties can be used both genetic information. for the reconstruction of geological processes and for specific technical applications. Although quartz research has a long history, the The SiO2 system and the structure of quartz questions concerning its chemical and physical Silica (SiO2), in at least 14 modifications, makes properties are far from being answered comple- up 12.6 wt.% of the Earth’s crust as crystalline tely. Modern analytical methods, especially those and amorphous silica (Table 2). In addition, the allowing analysis with low detection limits or dense orthorhombic silica polymorph ‘’ spatiallyresolved analyses(e.g. trace elements, O was first described bySharp et al. (1999) in SNC isotopes, paramagnetic defects, cathodolumines- meteorites (shergottites). In respect of its occur- cence), have generated much new mineralogical rence in nature and the amount of technical and geochemical data concerning the origin of material used, quartz is the most important silica

TABLE 2. The SiO2 system (modified after Strunz and Tennyson, 1982).

Quartz-- group (atmospheric and low pressure) Quartz trigonal High-quartz hexagonal Tridymite monoclinic High-tridymite hexagonal Cristobalite tetragonal High-cristobalite cubic Melanophlogite cubic Fibrous SiO2 (syn.) orthorhombic monoclinic

Keatite-- group (high and ultrahigh pressure) (syn.) tetragonal Coesite monoclinic Stishovite tetragonal Seifertite orthorhombic

Lechatelierite- group (amorphous phases) natural silica glass Opal water bearing, solid SiO2 gel

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modification. At 573ºC, trigonal a-quartz trans- to its morphology, the so-called right-handed and forms reversiblyinto the hexagonal high-temp- left-handed quartz crystals are distinguishable by erature quartz. The lattice parameters for low- and the position of the trapezohedron face x to the high-temperature quartz are those following positive main rhombohedron r (Fig. 1c). In (Strunz and Tennyson, 1982): addition, twinning of quartz is common, and the development of certain growth phenomena such Low quartz: trigonal-trapezohedral. a = 4.91 A˚ , c = 5.41 A˚ (Fig. 1), SiÀO spacing 1.61 A˚ ,OÀO as quartz with macro-mosaic and lamellar spacing 2.65 A˚ ,SiÀSi spacing 3.04 A˚ ,SiÀOÀSi structure (Friedlaender and Bambauer quartz angle 144º; lattice energy12967 to 15043 kJ mol À1, respectively), faden or sceptre-like growth, Mohs hardness 7, specific gravity2.65 g cm À3; skeletal or doublyterminated crystalscan be observed in natural quartz. (Rykart, 1989; High quartz: hexagonal-trapezohedral. a = 5.00 A˚ , Blankenburg et al., 1994). c = 5.46 A˚ (Fig. 1), SiÀO spacing 1.60 A˚ ,OÀO Quartz crystals with the ideal structure are spacing 2.65 A˚ ,SiÀSi spacing 3.03 A˚ ,SiÀOÀSi practicallynon-existent. Therefore, the properties angle 153º; lattice energy13596 kJ mol À1, of quartz are determined byits actual structure. Mohs hardness 7, specific gravity2.51 g cm À3. The type and frequency of lattice defects are influenced bythe thermodynamicconditions The of a-quartz is composed during mineralization. In addition, subsequent 4À exclusivelyof [SiO 4] tetrahedra with all Os processes such as changes of P-T conditions joined together in a three-dimensional network. during metamorphism or natural irradiation can Thus, the formula is SiO2 and the atoms are change the original structure of quartz. The lattice arranged in a trigonal symmetry. The c axis is defects can be classified according to their identical with the optical axis; perpendicular to it structure and size as follows: point defects there is the circular section of optical isotropy. As (zero-dimensional, <10À30 A˚ ); dislocations

FIG. 1. Schematic structure of quartz: (a) elementarycell of low-quartz; ( b) structure and typical morphology of low- quartz (left) and high-quartz (right); (c) chains of tetrahedra and typical morphology of left-handed (left) and right- handed quartz (right).

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(linear defects); subgrain or twin boundaries (two- small ionic radius of Si4+ and its high valence. dimensional); and three-dimensional defects due The most common trace-element-related para- 0 to microinclusions of minerals and fluids. magnetic centre in quartz is the [AlO4] centre which is caused bysubstitution of Si 4+ byAl 3+ with an electron hole at one of the four nearest Point defects in quartz O2À ions (Griffiths et al., 1954). The precursor + 0 Point defects in quartz can be related to the state for this centre is the diamagnetic [AlO4/M ] incorporation of foreign ions (e.g. Al, Ti, Ge, Fe, centre with an adjacent charge compensating H, Ag, Cu, P) in lattice and interstitial positions, cation (M+ =H+,Li+,Na+) in an interstitial + 0 to different types of displaced atoms, and/or to position. The [AlO4/M ] centre can be converted defects associated with Si or O vacancies. byX-raysor g-irradiation into the opticallyactive 0 According to their characteristics, these defect [AlO4] centre, resulting in the formation of centres are often classified as either intrinsic or smokyquartz (O’Brien, 1955; Cohen, 1956). extrinsic. Intrinsic point defects involve atoms of Other common trace-element centres in quartz the host lattice only(missing atoms = vacancies, are associated with the incorporation of Ti, Ge atoms at interstitial positions, and excess atoms), and Fe (Weil, 1984, 1993). Additionally, a whereas extrinsic point defects belong to foreign hydrogenic trapped hole-centre with four H atoms in lattice and inter-lattice positions. atoms at a Si site was reported byNuttall and + 0 Furthermore, the defects can be divided, Weil (1981). Centres of the type [TiO4/Li ] are according to their electronic structure, into two produced byirradiation of the diamagnetic 0 3+ classes À diamagnetic and paramagnetic. The precursor [TiO4] (Ti , i.e. electron centre at presence and structure of such defect centres can Ti4+). This precursor is formed bysubstitution of be analysed by means of electron paramagnetic Ti4+ for Si4+ at the Si position, where charge resonance (EPR) in combination with trace- compensation is achieved bya Li + ion at a element analysis and a variety of spectroscopic channel position nearby(Wright et al., 1963; methods (e.g. luminescence, UV-Vis-IR absorp- Rinneberg and Weil, 1972). The Ge centre is of tion). Up to the present, >20 different types of the same type as the Al centre. Substitution of point defects in quartz have been detected (e.g. Si4+ byGe 4+ causes formation of the diamagnetic 0 Kostov and Bershov, 1987; Weil 1984, 1993; precursor [GeO4] , which transforms into the À Stevens-Kalceff et al., 2000). The most common paramagnetic [GeO4] during g-irradiation. At defect types in quartz are shown schematically in room temperature, these centres can bind Fig. 2. diffusing M+ cations, preferentiallyforming + 0 + 0 Table 3 illustrates that the number of ions [GeO4/Li ] and [GeO4/H ] (Mackey, 1963; substituting for Si is small. This is due to the Rakov et al., 1985; Weil, 1993). Some Fe3+

FIG. 2. Schematic quartz structure showing the most common defect types.

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TABLE 3. Most common paramagnetic defects in quartz (modified after Plo¨tze, 1995).

Foreign ion centres Vacancies Si4+ Interstitial substitution vacancyvacancy

À Metastable electron [TiO4] E’ centres: + 0 + + + 3À centres [TiO4/M ] M =H,Li [SiO3] À À (+e ) [GeO4] + 0 + + + [GeO4/M ] M =H,Li

0 À defect electron [AlO4] O centres: À 0 À 3À centres (Àe ) [FeO4] O ,O2 , 3À + O2 ÀM

+ 0 + + + Stable [FeO4/M ] M =H,Li À 3+ (paramagnetic [FeO4] ?Fe without charge (precursor 0 receive) for [FeO4] )

paramagnetic centres mayoccur in quartz. One of peroxylinkage ( :SiÀOÀOÀSi:)andthe these defects is characterized bythe substitution peroxyradical ( :SiÀOÀO) (Friebele et al., of Fe3+ for Si4+ with charge compensation by 1979; Baker and Robinson, 1983). Furthermore, alkali ions or protons À so-called S centres [FeO4/ H excess from the H2O crystallization medium M+]0 (Stegger and Lehmann, 1989; Mineeva et can result in the formation of OHÀ centres in al., 1991). quartz (silanol groups). This defect consists of a Other types of defects can be attributed to O proton bound on a regular lattice O of the SiO4 and Si vacancies (Table 3). The group of tetrahedron (Weil, 1984). The resulting negative O-deficient centres (ODC) comprises the neutral net charge maybe compensated byan additional O vacancy( :SiÀSi:)andtheE’ centres silanol group or a trivalent substitute in Si4+ (Nishikawa et al., 1994). The ODC is diamagnetic position (e.g. Al3+). and can be detected byluminescence spectro- Up to the present, several attempts have been scopy. The paramagnetic E’1 centre is formed by made to relate specific paramagnetic defects to an O2À vacancyresulting in the transformation of certain genetic conditions of quartz formation. an O tetrahedron into a planar arrangement of One of the first attempts was made byDennen et three O ions (Weeks, 1956). In consequence, the al. (1970), who proposed a geothermometer based centre comprises an unpaired electron in a on the incorporation of Al into quartz as a dangling sp3 orbital of a single Si atom bound function of temperature of formation. Based on to these three O atoms. The centre can exist in this thermometer, Agel and Petrov (1990) used 0 0 three different stages E 1,E’1 and E’’1 (Griscom, the concentration of [AlO4] defects to calculate 1985), corresponding to its thermal stabilityand the crystallization temperature of quartz grains to the reactivitywith respect to irradiation. from deep-drilling samples. On the other hand, OxygenÀ centres represent different types of primarydefect centres maybe thermallyhealed defect electrons on O in tetrahedra with Si bygeological processes. Bershov et al. (1975) 0 vacancies. The non-bridging oxygen hole centre reported a decreasing number of [AlO4] defects (NBOHC: :SiÀO·) represents the simplest in samples of the Eldjzhurtinski granite with elementaryO-related intrinsic defect in quartz. increasing depth and temperature. At a depth of This centre can be described as the O part of a 1850 m ( T= 112ºC), these types of defect centres broken bond (Griscom, 1985). Precursors of the disappeared totally(Fig. 3). The authors 0 À NBOHC can be strained regular SiÀO bonds as concluded that [AlO4] and [TiO4] centres may well as peroxylinkages, silanol groups or Si- be used as indicators of temperature during burial. alkali bonds (Stevens-Kalceff et al., 2000). The frequencyof specific defect centres seems Oxygen excess centres in quartz include the also to show a genetic dependence. High

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+ 0 concentrations of [TiO4/H ] centres were of raw materials, manufacturing processes, detected in metamorphic quartz, whereas [TiO4/ irradiation, mechanical stress, temperature, and Li+]0 centres are typical for quartz in igneous the presence of impurities, influence the type and rocks (Rakov and Milovidova, 1991; Agel, 1992; number of defects. Furthermore, new defects may Plo¨tze, 1995). Quartz from pegmatites is, in be formed and existing defects transformed into general, characterized bysmall concentrations of other defect types. Therefore, the analysis of point pure lattice defects and onlyshows elevated defects is essential for the use of quartz and silica contents of trace-element-related point defects materials in several highly-advanced technical (Go¨tze et al., 2004). In addition, investigations of applications. For instance, different kinds of paramagnetic centres in and related quartz defects lead to electrical instabilities in SiO2 byGo¨tze et al. (1999) revealed that the frequency insulator layers and lower the quality of optical 3À of E’ and O2 centres varies between agates from materials due to loss bydispersion and absorption acidic and basic volcanic host rocks (Fig. 4). effects. Poor qualityin Piezo quartz can arise Furthermore, different centre types may be from absorption effects and from elevated indicative of certain ore deposits or certain quartz- concentrations of OH-centres which mayorigi- bearing igneous rocks and, thus, of provenance nate from the aqueous crystallization medium. (e.g. Plo¨tze, 1995; Go¨tze and Plo¨tze, 1997; Go¨tze Furthermore, incorporation of Al during crystal and Zimmerle, 2000; Go¨tze et al., 2004). The growth can limit significantlythe application of 0 concentration of [AlO4] defects in quartz, for optical quartz because of possible colouring instance, correlates with the Au and Ag content in during natural or artificial radiation (formation quartz-bearing rocks, making it applicable to of smokyquartz). prospecting for noble-metal deposits (Matyash et al., 1987). Botis et al. (2006) and Pan et al. (2006) showed that the distribution of radiation-induced centres in quartz provides information about the Characterization of point defects in quartz timing and source of U mineralization and also using cathodoluminescence (CL) traces paleo-pathways of U-bearing fluids. The great interest concerning luminescence The presence of defects in the quartz lattice can studies of quartz is based on the fact that change its structural, electrical and optical information, not available from other analytical properties strongly. Many factors, such as type methods, can be obtained. The close relationship

FIG. 4. Frequencyof paramagnetic defects related to O 0 À 3À FIG. 3. Concentration of [AlO4] and [TiO4] centres in and Si vacancies (E’ and O2 centres respectively) in quartz from the Eldjzhurtinski granite vs. depth and agates and related quartz incrustations from different temperature (modified after Bershov et al., 1975). volcanic rock types (modified after Go¨tze et al., 1999).

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between crystal-chemical properties and spectral measurements. In combination with luminescence characteristics is the basis upon electron spin resonance spectroscopyand spatially which to visualize the defect structure of quartz resolved trace-element analysis, the different and to reveal different growth generations, emission bands can be related to specific lattice internal structures or distribution of trace defects in the quartz structure (e.g. Stevens- elements within quartz (Fig. 5). On the other Kalceff et al., 2000; Go¨tze et al., 2001a). The hand, CL is an effective method for spatially defects causing the different CL emissions in resolved analysis of point defects in quartz by quartz often reflect the specific physico-chemical conditions of crystal growth and can, therefore, be used as a signature of genetic conditions of mineral formation. The typical CL of igneous and metamorphic quartz consists of two emission bands with maxima at 450 and 650 nm (Fig 5c), which are, in general, the most common emission bands in natural quartz (Go¨tze et al., 2001a;Go¨tze, 2009a). The different visible luminescence colours in quartz depend on the relative intensities of these two dominant emission bands. Most igneous quartz grains show luminescence colours in different shades of blue caused bythe predominance of the 450 nm emission. This 450 nm emission is due to the recombination of the so- called self-trapped exciton (Stevens-Kalceff and Phillips, 1995), an electron hole pair on an O vacancyand a peroxylinkage. Recent results have shown that the intensityof this emission is especiallyhigh in O-deficient SiO 2 samples (Skuja, 1998). In volcanic and metamorphic quartz, the intensityof the 650 nm emission band is often higher than in granitic quartz, resulting in a visible reddish-brown CL. The 650 nm emission is attributed to the recombination of electrons in the non-bridging O band-gap state, with holes in the valence-band edge (Siegel and Marrone, 1981). A number of different precursors of this NBOHC have been proposed, such as H- or Na-impurities, peroxylinkages (O-rich samples), or strained SiÀO bonds (Stevens-Kalceff and Phillips, 1995). The development of typical reddish grain rims in volcanic quartz results from the reaction of earlycrystallizedquartz crystals with the melt (Fig. 5b). This process leads to the generation of defects (bond breaking) in the reaction zone and thus to an increased 650 nm emission band. In metamorphic quartz,

FIG. 5. Polarized microscopy( a) and CL (b) micrograph mechanical deformation mayresult in bond pair of a quartz phenocryst in a rhyolite from Euba breaking and thus, in the formation of the (Saxony, Germany); the CL image reveals internal NBOHC. growth structures invisible with polarizing microscopy; The defect structure and luminescence beha- the related CL emission bands of different zones (c) viour of pegmatitic quartz differs from those of illustrate that the visible CL colour depends on the quartz from other origins (hydrothermal, igneous intensityratios of the two main emission bands at 450 and metamorphic quartz). Electron paramagnetic and 650 nm. resonance measurements revealed an almost

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complete lack of intrinsic lattice defects almost completelylacking, indicating that the associated with O or Si vacancies (e.g. the E’ defects responsible for these CL emissions are 3À centre or O2 centre), whereas some trace absent in pegmatitic quartz. elements (Al, Ti, Ge, Li) maybe enriched and Hydrothermal quartz crystals may show a form paramagnetic centres (Go¨tze et al., 2004). varietyof luminescence colours, sometimes Accordingly, the luminescence spectra are domi- arranged in distinct zoning. Several studies nated bya strong 500 nm emission, which can be showed that the CL characteristics of hydro- related to the alkali-compensated trace-element thermal quartz mayalso depend on the crystal- centres in the quartz structure (Ramseyer and lization temperature (Ioannou et al., 2003; Rusk et Mullis, 1990; Go¨tze et al., 2005). After electron al., 2008; Jourdan, 2008). At high temperatures bombardment, the intensityof the blue lumines- (>400ºC), a homogeneous blue luminescence cence emission falls off rapidlywithin 30 to 60 predominates, whereas at lower temperatures seconds (Fig. 6). This can be related to ionization- (<300ºC), strong zoning is common and yellow enhanced diffusion of luminescence centres as CL can be observed. was shown byRamseyerand Mullis (1990) by The transient blue CL emission at 390 nm is a electrodiffusion experiments. Other CL emission common feature of a-quartz crystallized from bands, which are characteristic features of aqueous solutions and was observed both in igneous, metamorphic or hydrothermal quartz natural and synthetic hydrothermal quartz speci- (e.g. those at 450 nm, 580 nm and 650 nm) are mens (Fig. 7). Therefore, both primaryhydro- thermal mineralization and secondary hydrothermal processes may be revealed by this characteristic CL emission. The 390 nm emission correlates well with the Al content and the + concentration of paramagnetic [AlO4/M ] centres in quartz (Alonso et al., 1983; Luff and Townsend, 1990; Perny et al., 1992; Gorton et al., 1996). Therefore, the alkali- (or H-) compensated + [AlO4/M ] centre has been suggested as being responsible for this deep blue emission band. The transient emission is verysensitive to irradiation damage, with a rapid attenuation of the emission intensityunder an electron beam, which results from the dissociation and electromigration of the charge-compensating cations out of the interac- tion volume under the influence of the irradiation- induced electrical field. The typical decrease of the blue CL emission band under the electron beam is often accompanied byan increase of the 650 nm emission caused bythe conversion of precursors (e.g. SiÀOH silanol groups from the mineralizing fluid) into the non-bridging O centres due to electron irradiation. This is visible bya change in CL colour from an initial blue to brownish (Fig. 7). The other typical luminescence band in hydrothermal quartz is the yellow emission at 580 nm. Go¨tze et al. (1999, 2001a) detected the yellow CL emission predominantly in agates of acidic volcanics and hydrothermal quartz (Fig. 7). FIG. 6. CL image and related CL emission spectra of Since those quartz samples also have a veryhigh quartz from pegmatite (Frikstad, Norway); the intensity content of lattice defects (especiallylarge of the CL emission stronglydecreases under electron concentration of O vacancies, i.e. E’1 centres), irradiation (see inset) due to the interaction of the these defects maybe responsible for the yellow luminescence centres with the electron beam. CL emission band at 580 nm. The close

652 PROPERTIES AND APPLICATIONS OF QUARTZ

FIG. 7. CL images and related emission spectra of different kinds of hydrothermal quartz: (a) quartz crystal with initial CL; (b) CL after 60 seconds of electron irradiation showing the change from blue to brownish; (c) displays the opposite behaviour of the ~400 nm and 650 nm emission bands; (d) sector zoned hydrothermal quartz crystal; (e) ; (f) yellow CL caused by an emission band around 580 nm.

relationship between this emission and large the common occurrence of the 580 nm emission concentrations of defect centres lead to the band in quartz can possibly be conclusion that this luminescence can be related related to rapid growth from a non-crystalline to processes of fast crystallization. For instance, precursor.

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FIG. 8. CL images of natural and artificial radiation damage in quartz: (a) yellow-orange luminescent radiation halo around a zircon inclusion in a quartz from granite; (b) related spectra of the host quartz and the damaged area with increasing 650 nm emission; (c) radiation rim in quartz due to artificial a-particle bombardment (modified from Krickl et al., 2008).

A high state of lattice damage can be attained their radiation rims in quartz from sandstones in radiation-damaged quartz (Habermann et al., and crystalline rocks. These rims are due to a- 1997; Krickl et al., 2008; Fig. 8). Such lattice particles, which create lattice damage when damage causes halos around U- and Th-bearing penetrating the quartz. The radiation haloes are accessoryminerals (e.g. zircon), which are not characterized bya strong increase in the 650 nm detectable byconventional polarizing micro- CL emission band (Fig. 8). The creation of scopy(Owen, 1988; Meunier et al., 1990; NBOHC defects is caused bybond breaking Ramseyer et al.,1988;Go¨tze et al., 2001a). As due to the a-particles, which was confirmed by well as recent and previous migration tracks of the radiation experiments of Komuro et al. U-bearing fluids, pores also can be identified by (2002) and Krickl et al. (2008). Botis et al.

654 PROPERTIES AND APPLICATIONS OF QUARTZ

(2005) reported pronounced CL emission bands Mu¨ller et al. (2000, 2002, 2003a) used quartz in the UV at ~350 nm and in the red region CL in combination with trace elements to (620À650 nm) in natural radiation-damaged reconstruct the geological evolution of granitic quartz. systems. Similar investigations were carried out The presented examples show that lumines- byVan den Kerkhof et al. (2004) to reveal details cence methods are useful in the detection and of quartz recoveryin a granulite from the Bamble interpretation of point defects in quartz. Specific sector, Norway. Furthermore, effects of shock luminescence emission bands can be related to damage in quartz due to impact events have been different defect centres. The relation between revealed byCL in terrestrial and extraterrestrial specific quartz crystallization or alteration samples (e.g. Sippel, 1971; Ramseyer et al., 1992; processes and the formation of characteristic Go¨tze, 2009a). The quartz crystals show features defects allows the recognition and reconstruction of micro-brecciation and shifts of the lumines- of different processes of mineral formation and cence emission bands under the influence of high alteration. pressure. Applications of the characteristic luminescence Cathodoluminescence studies can also help in properties of quartz are numerous. One of the first the recognition and reconstruction of applications was the evaluation of the provenance of detrital quartz grains in sands and sandstones (Sippel, 1968; Zinkernagel, 1978; Richter et al., 2003). Assuming that quartz from different parent rocks shows different CL signatures (colours), sediments with varying provenance can be distinguished. However, Boggs et al. (2002) have shown that the application of CL colours is sometimes problematic because quartz of different genesis might have similar CL colours. To avoid misinterpretations on the basis of initial or final CL colours, Go¨tte and Richter (2006) additionallyused the shift of the CL colour during electron irradiation as an indicator of provenance. Processes of compaction, brittle deformation, quartz cementation, and porosityevolution in the diagenetic historyof reservoir sandstones can also be evaluated using CL (e.g. Houseknecht, 1991; Millikan and Laubach, 2000). This information has also been used to characterize and distinguish different kinds of recent and ancient building sandstones (e.g. Michalski et al., 2002; Go¨tze and Siedel, 2004; Go¨tze et al., 2007). Cathodoluminescence is an outstanding method which can be used to reveal multiple processes of crystallization or secondary overprint, often not possible byother analyticalmethods. Several studies have shown, for instance, that the permineralization process of wood is often a multiple and complex process (e.g. Go¨tze and Ro¨ßler, 2000; Witke et al., 2004; Matysova´ et al., 2008; Go¨tze et al., 2008). Figure 9a shows an FIG. 9. Detection of multiple processes and secondary example from Chemnitz (Germany) of silicified overprint, respectivelyusing CL; ( a) silicified wood wood remains displaying silicification events: a from Chemnitz (Germany) showing parts of primary primarysilicification (yellowCL) and a silicification (yellow CL) penetrated by secondary secondaryhydrothermaloverprint (transient blue hydrothermal fluids (blue CL); (b) quartz grains from CL). The recognition of these two events was not the Witwatersrand conglomerate, RSA, showing radia- possible using conventional microscopy. tion rims due to migrating U-bearing fluids..

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mineralization processes in ore deposits (e.g. in an increasing ‘internal strain energy’ of the Rusk et al., 2006; 2008). Graupner et al. (2000, crystal. Therefore, ordering and disordering 2001) used the CL signatures of quartz from processes compete during deformation. barren metamorphic host rocks and Au-bearing Following deformation, ordering mechanisms parts of the giant Au deposit of Muruntau to prevail to lower the free energyand to shorten obtain information about the origin of the the length of dislocations in the crystal lattice À mineralizing fluids and the formation process of this is termed recovery. Processes of recovery the deposit. In the exploration of U deposits, the result, for example, in the formation of subgrain creation of radiation damage in quartz by boundaries (Fig. 11b; Passchier and Trouw, radioactive fluids can help to reveal U migration 1998). Cathodoluminescence can be used to pathways. Figure 9b presents a CL image with an displaythe microtextures of quartz grains due to example from the Au-U deposit of Witwatersrand, the dependence of the CL intensityon the number RSA. of local defects in the lattice. Figure 11c,d illustrates that the migration and concentration of point defects and dislocations can result in the accumulation of defects along grain and subgrain Dislocations and internal structures in quartz boundaries. These areas show high CL intensities. Dislocations in quartz are the most important line Dependent on the specific conditions of crystal- (one-dimensional) defects. The main types are lization and deformation, quartz mayexhibit a edge and screw dislocations (Fig. 10). Theyoften great varietyof internal structures, which can be originate from the condensation of point defects revealed bypolarizing microscopyor CL. during crystal growth or by mechanical and Crystallization from magma or solution mostly thermal influence. Therefore, the type and results in homogeneous, non-undulatoryquartz. number of dislocations is closelyconnected to However, growth zoning and sector zoning are the specific growth conditions. On the other hand, sometimes detectable using CL (compare Figs 5 dislocations mayresult from mechanical trig- and 7). Increasing pressure and temperature gering and/or rapid cooling after the growth during deformation will initiallycreate quartz process. with undulose extinction, followed bydeforma- Especiallyduring metamorphic processes, tion breaks between domains of undulatory deformation of a crystal can result in the extinction, formation of a polycrystalline aggre- movement of lattice defects. These moving gate with elongated crystal fabric follows, and vacancies or dislocations can cause relative finally a mosaic of polyhedral or polygonized displacements of crystal parts (intracrystalline quartz develops (Fig. 11). Accordingly, quartz deformation À Passchier and Trouw, 1998). The deformation is a continuum, with a systematic increasing number of induced dislocations results series of processes À deformation, recovery,

FIG. 10. Scheme of the most important line (one-dimensional) defects in quartz À edge (left) and screw dislocations (right).

656 PROPERTIES AND APPLICATIONS OF QUARTZ

primary recrystallization, and secondary recrys- reconstruct metamorphic processes or to recog- tallization (Passchier and Trouw, 1998). nize the origin of detrital quartz grains in Deformation is reflected opticallybyundulatory sedimentaryrocks (e.g. Folk, 1968; Voll, 1968; extinction, deformation lamellae and bands, Basu et al., 1975; Young, 1976; Basu, 1985; elongated crystal units, and sutured crystal- Passchier and Trouw, 1998). crystal boundaries (Fig. 11). Recovery is recog- In technical applications, line defects are often nized opticallybysegmented extinction (semi- visualized in two different ways: treatment with composite extinction) reflecting polygonization of etching techniques and X-raytopography the crystal. Primary recrystallization occurs when (Fig. 12). During etching, the projection points strain-free areas surrounded bydislocation tangles and lines caused bydislocations are attacked first form new crystals, and is recognized optically by due to their higher potential. The number of etch the presence of small (50 mm), non-undulatory pits correlates with the number of line defects. crystals. Secondary recrystallization develops Such natural etching features can also be used as large, non-undulatory strain-free polyhedral crys- diagnostic features for the specific environments tals with smooth crystal-crystal boundaries. The of natural quartz grains, especiallyin sedimentary knowledge surrounding the development of petrology(e.g. Krinsleyand Doornkamp, 1973; internal structures in quartz can be used to Le Ribault, 1977).

FIG. 11. Internal structures of quartz crystals reflecting different stages of metamorphic deformation and recovery: (a) elongated quartz grains from a gneiss showing undulose extinction and sutured grain boundaries; (b) redistribution of dislocations in a scheme of recoverywith development of undulose extinction, deformation bands and subgain boundaries (modified after Passchier and Trouw, 1998); (c,d) polarized light and CL images respecively, of quartz from a metamorphic host rock À the grain and subgrain boundaries are clearlyvisible in CL due to the accumulation of defects and the resulting high CL intensity.

657 J. GO¨ TZE

that quartz develops specific inclusion features depending on crystallization conditions. Mineral species included in igneous quartz are mainlyfeldspar, mica, rutile, zircon, Fe oxides, pyrite, cassiterite, wolframite, Nb-Ta minerals, etc. as well as silicic glass inclusions (Roedder, 1984; Leeder et al., 1987). Typical mineral inclusions in rhyolitic quartz are zircon, rutile, magnetite, ilmenite, hypersthene, aegirine, amphi- bole, biotite, tourmaline, apatite and fluorite (Thomas and Blankenburg, 1986; Mainley, 1996). Remarkable is the presence of OH-, F- and P-bearing minerals as well as volcanic glass, which are interpreted as representing products of FIG. 12. Hydrothermally etched (0001) plane of a an earlycrystallization(Clocchiatti, 1975; Hanson synthetic quartz crystal (left) and X-ray topography of et al., 1996). a synthetic quartz crystal (right) showing an almost The spectrum of mineral inclusions in meta- perfect core (crystal seed) and numerous line defects in morphic quartz depends on the conditions of the outer part of the crystal (modified after Blankenburg metamorphism. Whereas mineral inclusions of et al., 1994). chlorite, muscovite or amphibole are more characteristic of low-grade metamorphic rocks, kyanite, staurolite or occur especially in The quality of synthetic quartz crystals is often high-grade metamorphic rocks. In contrast, glassy checked byX-raytopography.This is a non- inclusions are rare in quartz of metamorphic destructive technique and is sensitive to minute origin (Wu¨nsch, 1987; Heynke, 1990; Gerler, distortions and changes in lattice constants; 1990). Inclusions of anhydrite, gypsum, poly- consequently, the method is used to study halite, calcite, several salt minerals, organic dislocations in almost perfect quartz crystals matter, etc. have been described in sedimentary- (Blankenburg et al., 1994). The example in authigenic quartz. The occurrence of these Fig. 12 shows a synthetic crystal with a nearly inclusions clearlydocuments the sedimentary defect-free core (seed crystal) and high defect environment of quartz growth (Richter, 1971; densityin the outer part (probablydue to Fruth and Blankenburg, 1992; Go¨tze, 2009b). inappropriate growth conditions). Mineral inclusions often form paragenetically with quartz, and are fingerprints of the crystal- lization environment. On the other hand, the type Mineral and fluid inclusions in quartz(three- and number of mineral inclusions influences dimensional defects) significantlythe trace-element composition of During quartz growth, three-dimensional defects quartz. Furthermore, even traces of refractory of mineralizing fluids or paragenetic minerals (or minerals (e.g. zircon, aluminosilicates) have to be exsolutions) can be included in quartz crystals. considered if quartz raw materials are to be used The shape and nature of inclusions in quartz were in melting processes (e.g. the glass industry). first described bySorby(1858), and since that The type, frequency, and composition of gas time have been used in genetic studies bymany and fluid inclusions, as well as fluid-inclusion authors. Numerous textbooks and publications thermometry, are important parameters used to deal with mineral and fluid inclusions in quartz reveal the genetic historyof quartz. Classical (e.g. Ermakov, 1950; Roedder, 1984; Sheperd et studies of gas and fluid inclusions in quartz are al., 1985; Leeder et al., 1987; Van den Kerkhof numerous (e.g. Ermakov, 1950; Roedder, 1984 and Hein, 2001). Inclusions provide information and references therein; Sheperd et al., 1985; about paragenetic minerals, temperature of forma- Leeder et al., 1987; London, 1985; Walderhaug, tion, chemistryof mineralizing fluids, etc. This 1994; Van den Kerkhof and Hein, 2001) so that information can be used for the reconstruction of quartz of different origins maybe distinguished mineral-forming processes and provides impor- using the distribution and physiography of tant data about impurities in raw materials. The inclusions, temperature of homogenization, and major point of interest is based on the observation chemical composition of fluid inclusions. Using

658 PROPERTIES AND APPLICATIONS OF QUARTZ

the distribution characteristics of the inclusions in glass. The conversion of quartz to cristobalite at the host mineral, it is often possible to distinguish 1400ºC depends stronglyon the number of fluid between gas-liquid inclusions of primary, pseudo- inclusions in the raw material (Gemeinert et al., secondaryand secondaryorigin. Primaryand 1992). Large numbers of fluid inclusions appear pseudo-secondaryinclusions both formed during to enhance the conversion of quartz to cristobalite primarymineral growth, however, the latter occur during thermal treatment. This maybe due to on (mostlyshort) healed microfractures. In decrepitation effects and the alkali elements (flux) contrast, secondaryinclusions clearlyformed within the inclusions. In contrast, the quartz type after quartz formation and occur on trails cross- and inclusions therein have almost no influence cutting all older microstructures. on the melting behaviour of raw materials for A careful thermometric and cryometric analysis silicate glasses, where the granulometric proper- of primarygas-fluid inclusions can provide ties appear to be more important (Go¨tze et al., minimum temperatures and minimum pressures 1993). of formation of the quartz, whereas micro- thermometric measurements on secondaryinclu- sions yield information concerning conditions of secondaryalteration of the host mineral. Tr a c e e l e m e n t s Additionally, results of modern analytical Quartz is one of the purest minerals in the Earth methods such as microchemical analysis, capil- crust. Nevertheless, trace-element contents are laryelectrophoresis, infrared spectroscopy, important geochemical parameters. Impurities in Raman spectroscopy, isotope measurements, the form of trace elements can either be INAA or LA-ICP-MS provide data concerning incorporated into the crystal structure or bound the chemical composition of fluid inclusions, to microinclusions (fluid or mineral inclusions). which can be used to distinguish inclusion Figure 14 illustrates that few elements are present characteristics of various formation environments in quartz in concentrations >1 ppm. As already (e.g. Klemm, 1986; Gerler and Schnier, 1989; mentioned, this is due to the limited number of Go¨tzinger, 1990; Ghazi et al., 1993; Hanson et al., ions which can substitute for Si4+ in the crystal 1996; Hallbauer, 1997; Channer et al., 1999; Flem lattice. The structural incorporation in a regular et al., 2002; Mu¨ller et al., 2003b;Go¨tze et al., Si4+ lattice position was proved for Al3+,Ga3+, 2004). Fe3+,Ge4+,Ti4+ and P5+ (e.g. Weil, 1984; 1993). Elevated contents of fluid inclusions in quartz Aluminium is the most frequent trace element can also influence the chemical composition and in quartz (up to a few 1000 ppm), which is due to qualityof quartz raw materials. Additionally,the its common occurrence in the Earth’s crust and type and number of fluid inclusions may influence the similar ionic radii of Si4+ and Al3+. In the case the melting behaviour of quartz. Figure 13 of Ti4+ and Fe3+, the relativelylarge ionic radii illustrates the thermal behaviour of different mayresult in the preferred incorporation in quartz types during the production of pure silica marginal parts of the crystals (Go¨tze and Plo¨tze, 1997), or exsolution phenomena (e.g. formation of rutile inclusions) at lower temperatures (Go¨tze et al., 2004). Other cations such as H+,Li+,Na+, K+,Cu+ or Ag+ can be incorporated in interstitial positions, sometimes acting as charge-compen- sating ions. Whereas Li seems to be more frequentlyincorporated into the quartz structure, Na and K mayalso be hosted byfluid inclusions (Go¨tze et al., 2004). Several authors have emphasized the role of H+ in the charge compensation of Al3+ÀSi4+ substitution (e.g. Bambauer, 1961; Miyoshi et al., 2005). The latter authors postulated that the replacement of 4+ 3+ + + FIG. 13. The dependence of the quartz-cristobalite phase Si byAl +H ÔLi is the principal transition at 1400ºC on the number of fluid inclusions mechanism for the structural incorporation of (FI) in used quartz raw materials (modified after these trace elements into hydrothermal quartz. Gemeinert et al., 1992). For most elements in quartz however, their

659 J. GO¨ TZE

FIG. 14. Average abundance and variations of trace elements in quartz (modified after Gerler, 1990 and Blankenburg et al., 1994).

presence in microinclusions is most important 1969; Lyakhovich, 1972; Suttner and Leininger, (e.g. Rossman et al., 1987; Gerler, 1990; Jung, 1972; Stenina et al., 1984; Hallbauer, 1992; 1992; Blankenburg et al., 1994; Monecke et al., Heynke et al., 1992; Go¨tze and Lewis, 1994; 2002a;Go¨tze et al., 2004). Gerler (1990), for Go¨tze and Plo¨tze, 1997; Monecke et al., 1999, instance, showed a strong correlation of the 2000; 2002a;Go¨tze and Zimmerle, 2000; Larsen elements Cl, Br, Na, Ca, Sr and Mn with the et al., 2000, 2004; Poutivcev et al., 2001; Mu¨ller water content of fluid inclusions, and concluded et al., 2002, 2003a,b, 2008; Go¨tze et al., 2004; that up to 100% of Cl, Br and I maybe Kostova et al., 2004; Go¨tze, 2009b). For genetic concentrated there. Other studies have revealed interpretations, the contrasting behaviour of that fluid inclusions mayhost a wide range of different trace elements in quartz has to be additional elements (e.g. Czamanske et al., 1963; considered. Elements such as Al, Ge, Li, REE Sucevskaya et al., 1970; Pickneyand Haffty, and the element ratios of Ge/Fe or Th/U appear to 1970; Malinko et al., 1976; Baranova et al., 1980; be reliable indicators of specific geological Naumov et al., 1984; Gerler and Schnier, 1989; settings. For instance, the 10Ge-Ti-Al/50 triangle Channer et al., 1999; Yardley et al., 1993; (Fig. 15) shows some general trends for different Klemm, 1994; Kostova et al., 2004). The results quartz types. Concentrations of other elements of Rossman et al. (1987), Ghazi et al. (1993) and (e.g. Be, Cs and Rb in Li-pegmatites or Nb and Ta Monecke et al. (2002a) suggest that along with in Nb-Ta pegmatites) do not reflect the specific Rb and Sr, the lanthanides are preferentially mineralization and, thus, cannot be used as hosted bythe fluid inclusions. On the other hand, petrogenetic indicators (Go¨tze et al., 2004). This the elements Ti, Al, K, Ca, Mg, Ba, Cs, Rb, Fe, fact has to be considered if trace elements in Cr, Co, Cu, Mn, Pb, Sc, W, U and the REE can quartz are to be used as pathfinder elements for also be related to microscopic mineral inclusions geochemical processes. in quartz (e.g. Gerler, 1990; Jung, 1992; Go¨tze et According to Schro¨n et al. (1982), quartz from al., 2004). earlycrystallizationstages is characterized bylow Despite the variable mechanisms controlling Ge/Fe ratios (large Fe content), whereas this ratio their incorporation into quartz, trace elements are is high in quartz from later generations. considered important petrogenetic indicators for Therefore, characteristic features of quartz from interpreting the conditions of mineral formation, pegmatites are large Ge and small Fe contents in order to reveal either the provenance of quartz, compared to quartz samples from other origins or to reconstruct the genesis of ore deposits and (Schro¨n et al., 1988, Go¨tze et al., 2004). Observed the origin of metal-bearing fluids (e.g. Bambauer, variations of the Ge/Fe ratio (4.5À0.1) can be 1961; Dennen, 1964, 1966, 1967; Walenczak, related to the crystallization sequence. The Ge

660 PROPERTIES AND APPLICATIONS OF QUARTZ

speciation is also illustrated in the 10Ge-Ti-Al/50 in hydrothermal quartz due to changing physico- triangle (Fig. 15), where pegmatitic quartz plots chemical conditions, crystallization effects, etc. within a field far from the trace-element Accordingly, the use of average trace-element composition of granitic and rhyolitic quartz contents for interpretation purposes maybe respectively. difficult. Jourdan (2008) showed that trace- Several studies have shown that the geological element variations are often accompanied by evolution and fractionation of granites and variations in isotopic composition. pegmatites is recorded in the trace-element The REEs also show a tendencyto create composition of quartz (Larsen et al., 2004; specific patterns related to the host rocks and the Jacomon, 2006; Mu¨ller et al., 2008). These last conditions of crystallization. The comparison of authors found differences in the trace-element REE contents of quartz from different geological composition (Al, Li, Fe, Ge and Ti) between syn- environments reveals marked differences in the and late-/post-orogenic pegmatites from Froland, chondrite-normalized distribution patterns Norway. Whereas the quartz from syn-orogenic (Fig. 16). The REE distribution pattern of pegmatites has a consistent trace-element signa- reflects a marine signature, which is similar to that ture, quartz from late- and post-orogenic pegma- of ocean water with a negative Ce anomaly. tites shows more variations in trace-element Quartz from granite is characterized bya crustal composition, i.e. a lowering of Li and Al and an signature with a negative Eu anomalydue to increase of Ti and Ge compared to syn-orogenic fractionation effects. In contrast, quartz from pegmatites. acidic volcanics often lacks the negative Eu Trends in trace-element composition can also anomalybecause of the earlycrystallizationof be observed in hydrothermal systems. Different quartz compared to feldspar. Metamorphic quartz temperatures of hydrothermal quartz formation is characterized bylow REE contents and a mayresult in different concentrations of Ti (large crustal signature without fractionation effects. concentration at high T) or Al (large concentration at low T) (e.g. Go¨tze et al., 2001b; Rusk et al., 2006, 2008; Jourdan, 2008). Furthermore, the formation of agate and chalcedonyoften results in the accumulation of elements such as Al, Ge, B and U from alteration processes of the surrounding volcanics (Go¨tze et al., 1999, 2001c). The results of these studies illustrate that there maybe a drastic trace-element zoning

FIG. 16. Chondrite-normalized REE distribution patterns FIG. 15. Characteristic trace-element ratios of quartz of quartz from different rock types; note the ‘tetrad from different host rocks in the 10Ge-Ti-Al/50-triangle effects’ in the REE distribution of quartz from pegmatite (modified and extended after Schro¨n et al., 1988). (modified and extended after Go¨tze, 1998).

661 J. GO¨ TZE

The position of pegmatitic quartz in the late larger concentrations of Al mayalso be present in stage of magmatic evolution often results in a form of microinclusions. On the other hand, pronounced negative Eu anomalyand ‘tetrad Mullis and Ramseyer (1991) discussed the role effects’ (Fig. 16). Recent results of Monecke et of tetrahedrallycoordinated Al in the mineralizing al. (2002b) showed that the convex tetrad effect fluid/melt for the structural incorporation into (i.e. 4 curves of REE groups) in samples from quartz. Evidentlyother factors, such as the magmatic environments can most likelybe number and type of compensating cations, or the explained byformation within the magma-fluid pH, have to be taken into account (Mullis and system before emplacement in the subvolcanic Ramseyer, 1991; Plo¨tze, 1995). More recent environment where phase separation causes a split studies, (Wark and Watson, 2006), have indi- of this system into fluid and magma subsystems. cated, that the incorporation of Ti into quartz may The negative Eu anomalyis also assumed to be a be an alternative route to reconstructing the characteristic feature of late magmatic fluids temperature of crystallization. (especiallyin evolved granitic systems),although Specific trace elements mayalso be used as there is no relationship between the intensityof indicators for ore mineralization. Figure 17 shows the Eu anomalyand the development of tetrad the REE distribution patterns of a barren effects (Monecke et al., 2002b). metamorphic host rock in comparison to quartz Knowledge of the specific trace-element from areas with a hydrothermal overprint and Sn features in quartz can be used for genetic mineralization. The REE signature clearlyreveals interpretations and the reconstruction of geolo- the hydrothermal overprint by mineralizing fluids. gical processes. As alreadymentioned, Dennen et Another example illustrates that the concentra- al. (1970) developed a geothermometer based on tions of Rb and Sr in quartz can be used to the Al concentration in quartz. Although the distinguish barren host rocks from those asso- results of Agel and Petrov (1990) confirmed the ciated with Sn or Au mineralization (Fig. 17). thermometer, Plo¨tze (1995) and Go¨tze et al. Last, but not least, trace elements are also (2001b) found no direct correlation between important criteria for the application of quartz raw temperature of quartz formation and the concen- materials in industry(e.g. Blankenburg et al., tration of Al or paramagnetic Al centres in quartz. 1994; Go¨tze, 1997; Mu¨ller et al., 2005). Iron and On one hand, there appears to be a saturation other elements have verysmall concentration concentration of ~400À500 ppm for the structural limits (Table 4). Especiallyin high-tech applica- incorporation of Al into quartz (Plo¨tze, 1995); tions (e.g. the optical industry) these conditions

FIG. 17. (a) REE distribution pattern in quartz of metamorphic host rocks compared to those from hydrothermally overprinted quartz in the exocontact to a Li-F granite with Sn mineralization; (b) Characteristic trace-element contents in metamorphic quartz of barren host rocks and related Sn- and Au-mineralizations respectively(modified from Monecke et al., 2002a).

662 PROPERTIES AND APPLICATIONS OF QUARTZ

TABLE 4. Chemical composition of high-purityquartz raw materials for different applications (data from Blankenburg et al., 1994).

Fibre optics Special optical Crystal Window Bottle glass glass glass glass

SiO2 >99.9 wt.% >99.8 wt.%

Fe2O3 <2.0 ppm <20 ppm <150 ppm <0.1 wt.% 0.5À4 wt.% TiO2 <1.5 ppm <25 ppm Al2O3 <500 ppm Cr2O3 <0.01 ppm <0.1 ppm CoO <0.05 ppm <0.05 ppm CuO <0.05 ppm <0.1 ppm MnO <0.1 ppm <1.0 ppm NiO <0.1 ppm <0.15 ppm V2O5 <0.5 ppm <15 ppm

can often onlybe fulfilled bysyntheticquartz the specific properties of the quartz raw material material. maydiffer widely.Therefore, different quartz types are being used in various industrial fields (Table 5). Industrial use of quartz One of the most important applications of Quartz is one of the most frequentlyoccurring quartz raw materials is their use as foundrysands minerals in the Earth’s crust with a relative in casting processes. Casting forms are prepared abundance of >12%. More than 90% of the total is using quartz sands with different binding agents found in igneous rocks. In contrast, more than such as clayand bentonite, water glass and/or 95% of quartz raw materials applied in the organic materials. The qualityof the casting industrycome from sedimentaryrocks. In forms depends stronglyon perfect interaction Germany, for instance, more than 80% of between the quartz grains and the binding industriallyused quartz raw materials are quartz material. Therefore, granulometric properties sands for the foundryand glass industry (grain size, grain shape, surface properties) play (Blankenburg et al., 1994). This fact clearly the most important role among the properties of shows that a strong dependence between the the quartz raw material. properties of quartz raw materials and the High-purityquartz sands are also the main raw properties for industrial use exists. Data materials for the production of silicate glasses. concerning quartz properties are necessaryto The amount of quartz maybe as high as 80 wt.% evaluate the usabilityof quartz raw materials, the in several glass products. Chemical purity limitations of processing and also the prognosis (prevention of glass colouring) and the grain- and search for new deposits (e.g. Blankenburg et size distribution (consistent melting behaviour) al., 1994; Go¨tze, 1997; Mu¨ller et al., 2005). are among the most important parameters for the Natural quartz raw materials represent a use of quartz in the glass industry(compare complex group of industrial rocks and minerals, Table 4). Sometimes the use of synthetic silica which are used as single crystals and polycrystal- raw materials is preferred in the case of high- line material or mono-mineralic rocks in the puritysilica glasses. industry. The applications of quartz are wide- During the 1950s, the need for perfectly spread, including its use as a bulk product (e.g. crystalline and extremely pure quartz crystals quartz sands in the foundryand glass industryor (e.g. Al <1 ppm) in modern technologies resulted quartzite for refractorymaterials), and perfect in the development of hydrothermal quartz crystals (piezo- and optical quartz), as well as Si synthesis (e.g. Nacken, 1950; Mosebach, 1955). ore for the production of Si alloys or semi- Although quartz frequentlyoccurs in nature, the conductor Si (Blankenburg et al. 1994). In all qualityof most natural quartz is too low to satisfy these applications, the requirements concerning the requirements for optical and piezo quartz.

663 J. GO¨ TZE

TABLE 5. Interrelation between genesis and specific properties of different quartz types and their preferred application in the industry.

Quartz type Properties Preferred application

Magmatic/postmagmatic Quartz of alaskite chemical high-puritysilica puritysynthetic (‘Iota quartz’) material Pegmatitic and chemical purity, optical and piezo quartz, Hydrothermal quartz perfect crystal order quartz synthesis (‘lascas’) solar silicon

Metamorphic Quartzite SiO2 up to >98% refractorymaterials Metamorphogenic mobilizates chemical purityquartz (‘lascas’) synthesis

Sedimentary Quartz sands chemical purity, glass and foundry industry, granulometric properties cristobalite, quartz powder Sedimentaryquartzite chemical purity, refractorymaterials cryptocrystalline silica

Outstanding optical and electrical properties such impuritycontents, such as high puritypegmatitic as refractive index, dispersion, optical activity, and hydrothermal quartz can be used as raw piezoelectricityor the transparencyfrom 150 to materials (the so called ‘lascas’) for crystal 3000 nm are being used in several high-tech growth. applications. Some 1000 t/y of synthetic hydro- All these examples show that the knowledge of thermal quartz crystals (Fig. 18) are currently the interrelation between quartz genesis À specific produced worldwide in autoclaves at 350À400ºC properties À parameters for technical application and 100À120 MPa. Onlyquartz with verylow is necessaryfor the successful use of quartz raw materials in manyindustrial applications.

Conclusions The knowledge surrounding quartz, one of the most frequent minerals of the Earth’s crust, has been stronglyincreased due to the development and application of advanced analytical methods. In recent years, techniques with low detection limits and/or high spatial resolution have provided a wealth of new data concerning the real structure and chemistryof natural and syntheticquartz. Quartz is characterized byspecific properties (indicator properties) À ranging from point defects up to macroscopic crystal shape À all of which are dependent on the geological historyand specific conditions of formation. Thus, investiga- tions concerning the typomorphic properties of FIG. 18. Synthetic quartz crystal (a) grown under quartz help to reveal the relations between quartz hydrothermal conditions (350À400ºC, 100À120 MPa) genesis, specific properties and industrial use. in an autoclave; note the development of crystal faces These data mayhelp to reconstruct the geological which is different from that of natural quartz crystals; historyand to determine the viabilityof a possible (b) indication of the crystal faces of synthetic quartz. industrial application.

664 PROPERTIES AND APPLICATIONS OF QUARTZ

Acknowledgements Krinsley, D. and Seyedolali, A. (2002) Is quartz cathodoluminescence color a reliable provenance The reviews of Th. Go¨tte (Bochum) and an tool? A quantitative examination. Journal of anonymous reviewer, which improved the quality Sedimentary Research, 72, 408À415. of an earlier version of the manuscript, are Botis, S., Nokhrin, S.M., Pan, Y., Xu, Y. and Bonli, T. gratefullyacknowledged. (2005) Natural radiation-induced damage in quartz. I. Correlations between cathodoluminescence colors and paramagnetic defects. The Canadian References Mineralogist, 43, 1565À1580. Agel,A.(1992)Paramagnetic defect centres in Botis, S., Pan, Y., Bonli, T., Xu, Y., Sopuck, V. and polycrystalline quartz of granitic and metamorphic Nokhrin, S. (2006) Natural radiation-induced origin. PhD thesis, Philipps UniversityMarburg, damage in quartz. II. Implications for uranium Germany, 109 pp. mineralization in the Athabasca basin. The Agel, A. and Petrov, I. (1990) Substitutional aluminium Canadian Mineralogist, 44, 1387À1402. in the quartz lattice as indicator for the temperature Channer, D.M.DeR., Bray, C.J. and Spooner, E.T.C. of formation. European Journal of Mineralogy, 2, (1999) Integrated cation-anion/volatile fluid inclu- Bh.1, 144. (in German). sion analysis by gas and ion chromatography; Alonso, P.J., Halliburton, L.E., Kohnke, E.E. and methodologyand examples. Chemical Geology, Bossoli, R.B. (1983) X-rayinduced luminescence 154,59À82. in crystalline SiO2. Journal of Applied Physics, 54, Clocchiatti, R. (1975) Les inclusions vitreuses des 5369À5375. cristaux de quartz. E´ tude optique, thermo-optique Baker, J.M. and Robinson, P.T. (1983) EPR of a new et chimique. Applications ge´ologiques. Me´moires À defect in natural quartz: possiblyO 2 . Solid State Societe´ Ge´ologique France, 122,1À96. Communications, 48, 551À554. Cohen, A.J. (1956) Color centers in alpha-quartz. Part I. Bambauer, H.U. (1961) Spurenelemente und Smokyquartz. Journal of Chemistry and Physics, 25, g-Farbzentren in Quarzen aus Zerrklu¨ften der 908À914. Schweizer Alpen. Schweizerische Mineralogische Czamanske, G.K., Roedder, E. and Burns, F. (1963) Petrographische Mitteilungen, 41, 335À367. Neutron activation analysis of fluid inclusions for Baranova, N.N., Kozerenko, S.V., Grigorian, S.S., copper, manganese, and zinc. Science, 140, Daryna, T.G. and Saveljev, B.V. (1980) 401À403. Experimental results about concentrations of gold Dennen, W.H. (1964) Impurities in quartz. Geological and silver in hydrothermal solutions Geokhimiya, 8, Society of America Bulletin, 75, 241À246. 146À157. (in Russian.). Dennen, W.H. (1966) Stoichiometric substitution in Basu, A. (1985) Reading provenance from detrital natural quartz. Geochimica et Cosmochimica Acta, quartz. Pp. 231À248 in: Provenance of arenites 30, 1235À1241. (G.G. Zuffa, editor). Reidel, Dordrecht, The Dennen, W.H. (1967) Trace elements in quartz as Netherlands. indicators of provenance. Geological Society of Basu, A., Young, S.W., Suttner, L.J., James, W.C. and America Bulletin, 78, 125À130. Mack, G.H. (1975) Re-evaluation of the use of Dennen, W.H., Blackburn, W.H. and Quesada, A. undulatory extinction and polycrystallinity in detrital (1970) Aluminum in quartz as a geothermometer. quartz for provenance interpretation. Journal of Beitra¨ge Mineralogie Petrologie, 28, 332À334. Sedimentary Petrology, 45, 873À882. Ermakov, N.P. (1950) Research on the nature of Bershov, L.V., Krylova, M.D. and Speranskij, A.V. mineral-forming solutions. Universityof Kharkov (1975) The electron hole centres OÀAl and Ti3+ as Press, Kharkov, Russia, 460 pp. (in Russian). indicator for temperature conditions during regional Flem, B., Larsen, R.B., Gromstvedt, A. and Mansfeld, J. metamorphism. Izvestiya Akademii Nauk SSSR, (2002) In situ analysis of trace elements in quartz by Seria Geologiya, 10, 113À117. (in Russian). using laser ablation inductivelycoupled plasma mass Blankenburg, H.-J., Go¨tze, J. and Schulz, H. (1994) spectrometry. Chemical Geology, 182, 237À247. Quarzrohstoffe. Deutscher Verlag fu¨ r Folk, R.L. (1968) Petrology of Sedimentary Rocks. Grundstoffindustrie, Leipzig-Stuttgart, Germany, Hemphill, Austin, Texas, USA, 170 pp. 296 pp. Friebele, E.J., Griscom, D.L., Stapelbroek, M. and Blatt, H., Middleton, G.V. and Murray, R.C. (1980) Weeks, R.A. (1979) Fundamental defect centers in Origin of Sedimentary Rocks. 2nd edition. Prentice- glass: the peroxyradical in irradiated, high-purity, Hall, Inc., Englewood Cliffs, New Jersey, USA, fused silica. Physical Review Letters, 42, 782 pp. 1346À1348. Boggs Jr., S., Kwon, Y.I., Goles, G.G., Rusk, B.G., Fruth, M. and Blankenburg, H.-J. (1992)

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